For improving the utilization and anti -poisoning performance of Pd catalysts for formate oxidation, atomic layer deposition (ALD) method was used to deposit Pd on carbon nanotubes (CNTs) and CNTs-supported Ag (Ag/CNTs). The structures of the as-prepared Pd/CNTs and Pd-on-Ag/CNTs catalysts were characterized using X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM). Electrochemical characterization and high -angle annular dark-field scanning TEM (HADDF-STEM) confirmed the Pd-on-Ag structure. Pd utilization, activity, and anti-poisoning performance for Pd/CNTs and Pd-on-Ag/CNTs catalysts were compared, indicating that the overall performances of the Pd-on-Ag catalysts are superior to those of Pd on CNTs without Ag. Particularly, the mass specific chronoamperometric current (I-cA) of the Pd-on-Ag/CNTs (171.8 mA mgpd (1)) is two times greater compared to that of Pd/CNTs (70.0 mA mgpd (1)). X-ray photoelectron spectroscopy (XPS) was used to explain the improved anti -poisoning performance from the aspect of electronic Pd-Ag interaction. The results in this paper demonstrated the need for rationally engineered supports for improving the anti poisoning performance of Pd-based anode catalysts. (C) 2016 Elsevier Ltd. All rights reserved.